Shampoo compositions comprising a chelant

ABSTRACT

Described herein is a shampoo composition and methods of using the same, the shampoo composition including a copper chelant, a detersive surfactant, and a carrier.

FIELD OF THE INVENTION

Described herein are shampoo compositions comprising a detersivesurfactant, a chelant, and a carrier, wherein the shampoo compositioninhibits both deposition/penetration of copper salts and othertransition metal salts in the hair and removes such salts from hairfiber. A method of cleansing hair with such shampoo compositions is alsodescribed herein.

BACKGROUND OF THE INVENTION

Many water sources that are used by consumers for personal care containelevated levels of calcium and magnesium salts, as well as undesirablelevels of redox metals (e.g., copper and/or iron) salts. As such, usingchelants to sequester trace redox metals often proves to be ineffectivebecause most chelants also competitively bind calcium and/or magnesium.

It has been found that even trace quantities of copper can deposit onthe hair surface and in between the cuticle layers of hair. Thisdeposition of copper on hair is especially problematic becausetransition metal ions, such as copper and iron, can facilitatereduction-oxidation (redox) reactions during hair coloring treatmentsand during UV exposure. These reactions generate reactive oxygen species(ROS), which in turn can cause damage to the hair. In addition, they caninterfere with the oxidative color formation chemistry and lead toreduced color uptake for hair colorant users.

Accordingly, there is a need for improved shampoo compositions that caninhibit copper depositing on hair, as well as facilitate the removal ofcopper already deposited thereon.

SUMMARY OF THE INVENTION

Described herein is a shampoo composition comprising:

(a) from about 0.005% to about 5% of one or more chelants, by weight ofthe shampoo composition, wherein the one or more chelants have amolecular structure as follows:

-   -   wherein n is 2 or 3; m is 1, 2, 3, or 4; and    -   Y and Z are independently selected from the group consisting of        hydrogen, methyl, ethyl, propyl, butyl, pentyl, —CH₂CH₂OH,        —CH₂CH(CH₃)OH), —CH₂CH₂NH₂, —CH₂CH(CH₃) NH₂, and combinations        thereof;    -   and wherein the one or more chelants comprise:        -   (1) log of the formation constant log K_(ML) of its complex            with copper is higher than 6;        -   (2) log P value is from about −5 to about 2; and        -   (3) molecular weight of from about 50 to about 500;            (b) from about 2% to about 50% of one or more detersive            surfactants, by weight of the shampoo composition; and            (c) from about 75% to about 98% of an aqueous carrier, by            weight of the shampoo composition;            wherein the shampoo composition has a pH of about 3 to about            8.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims particularly pointing outand distinctly claiming the invention, it is believed that the shampoocomposition described herein will be better understood from thefollowing description.

As used herein, the term “fluid” includes liquids and gels.

As used herein, the term “log x” refers to the common (or decadic)logarithm of x.

As used herein, the articles including “a” and “an” when used in aclaim, are understood to mean one or more of what is claimed ordescribed.

All percentages are by weight of the total composition, unless statedotherwise. All ratios are weight ratios, unless specifically statedotherwise. All ranges are inclusive and combinable. The number ofsignificant digits conveys neither a limitation on the indicated amountsnor on the accuracy of the measurements. The term “molecular weight” or“M.Wt.” as used herein refers to the weight average molecular weightunless otherwise stated. “QS” means sufficient quantity for 100%.

As used herein, “mixtures” is meant to include a simple combination ofmaterials and any compounds that may result from their combination.

All numerical amounts are understood to be modified by the word “about”unless otherwise specifically indicated. Unless otherwise indicated, allmeasurements are understood to be made at 25° C. and at ambientconditions, where “ambient conditions” means conditions under about oneatmosphere of pressure and at about 50% relative humidity. All suchweights percents (wt %) as they pertain to listed ingredients are basedon the active level and do not include carriers or by-products that maybe included in commercially available materials, unless otherwisespecified.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

Herein, “comprising” means that other steps and other ingredients whichdo not affect the end result can be added. This term encompasses theterms “consisting of” and “consisting essentially of”. The compositions,methods, uses, kits, and processes of the shampoo composition describedherein can comprise, consist of, and consist essentially of the elementsand limitations of the invention described herein, as well as any of theadditional or optional ingredients, components, steps, or limitationsdescribed herein. As used herein, the terms “include,” “includes,” and“including,” are meant to be non-limiting and are understood to mean“comprise,” “comprises,” and “comprising,” respectively.

The term “substantially free from” or “substantially free of” as usedherein means less than about 1%, or less than about 0.8%, or less thanabout 0.5%, or less than about 0.3%, or about 0%, by total weight of thecomposition.

“Hair,” as used herein, means mammalian hair including scalp hair,facial hair and body hair, particularly on hair on the human head andscalp.

“Cosmetically acceptable,” as used herein, means that the compositions,formulations or components described are suitable for use in contactwith human keratinous tissue without undue toxicity, incompatibility,instability, allergic response, and the like. All compositions describedherein which have the purpose of being directly applied to keratinoustissue are limited to those being cosmetically acceptable.

“Derivatives,” as used herein, includes but is not limited to, amide,ether, ester, amino, carboxyl, acetyl, acid, and/or alcohol derivativesof a given compound.

“Polymer,” as used herein, means a chemical formed from thepolymerisation of two or more monomers, which may be the same ordifferent. The term “polymer” as used herein shall include all materialsmade by the polymerisation of monomers as well as natural polymers.

Polymers made from only one type of monomer are called homopolymers. Apolymer comprises at least two monomers. Polymers made from two or moredifferent types of monomers are called copolymers. The distribution ofthe different monomers can be calculated statistically orblock-wise—both possibilities are suitable for the shampoo composition.Except if stated otherwise, the term “polymer” used herein includes anytype of polymer including homopolymers and copolymers.

The term “charge density” as used herein, means the ratio of the numberof positive charges on a monomeric unit of which a polymer is comprisedto the M.Wt. of said monomeric unit. The charge density multiplied bythe polymer M.Wt. determines the number of positively charged sites on agiven polymer chain. For cationic guars, charge density is measuredusing standard elemental analysis of percentage nitrogen known to oneskilled in the art. This value of percentage nitrogen, corrected fortotal protein analysis, can then be used to calculate the number orequivalence of positive charges per gram of polymer. For the cationiccopolymers, the charge density is a function of the monomers used in thesynthesis. Standard NMR techniques know to one skilled in the art wouldbe used to confirm that ratio of cationic and non-ionic monomers in thepolymer. This would then be used to calculate the number or equivalenceof positive charges per gram of polymer. Once these values are know, thecharge density is reported in milliequivalence (meq) per gram ofcationic polymer.

The term log P is the n-octanol/water partition coefficients of thematerial.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore, do not include carriers or by-products thatmay be included in commercially available materials.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

Shampoo Composition

Described herein is a shampoo composition comprising (a) from about0.005% to about 5% of one or more chelants; (b) from about 2% to about50% of one or more detersive surfactants, by weight of the shampoocomposition; (c) from about 75% to about 98% of an aqueous carrier, byweight of the shampoo composition, wherein the shampoo composition has apH of about 3 to about 8, and wherein the shampoo inhibits copperdeposition on hair and facilitates the removal of copper deposited onhair. The shampoo composition also delivers consumer desired shampooingin addition to inhibiting the deposition of copper (i.e. from the waterused to rinse) on the hair.

A. Chelants

The shampoo composition comprises from about 0.005% to about 5%,alternatively from about 0.01% to about 3%, alternatively from about0.01% to about 1%, alternatively from about 0.01% to about 0.5%,alternatively from about 0.01% to about 0.1%, and alternatively fromabout 0.025% to about 0.05% of one or more chelants by weight of theshampoo composition, wherein the one or more chelants have a molecularstructure as follows:

-   -   wherein n is 2 or 3; m is 1, 2, 3, or 4; and    -   Y and Z are independently selected from the group consisting of        hydrogen, methyl, ethyl, propyl, butyl, pentyl, —CH₂CH₂OH,        —CH₂CH(CH₃)OH), —CH₂CH₂NH₂, —CH₂CH(CH₃) NH₂, and combinations        thereof;    -   and wherein the one or more chelants comprise:        -   (1) log of the formation constant log K_(ML) of its complex            with copper is higher than 6;        -   (2) log P value is from about −5 to about 2; and        -   (3) molecular weight of from about 50 to about 500.            Stability Constants of Exemplary Chelants

The relative affinity of a chelant at a specified pH for Cu⁺² can beassessed by its Stability Constant. The Stability Constant of a metalchelant interaction is defined as:

$K_{ML} = \frac{\lbrack{ML}\rbrack}{\lbrack M\rbrack\lbrack L\rbrack}$where:[ML] is the concentration of metal ligand complex at equilibrium;[M] is the concentration of free metal ion;[L] is the concentration of free ligand in a fully deprotonated form;andK_(ML) is the stability constant for the metal chelant complex.

The stability constants of chelant-metal ion complexes are welldocumented in the literature for commonly used chelants (see, forexample, Arthur Martell & Robert M Smith, Critically Selected StabilityConstants of Metal Complexes Database, Version 3.0 and above,incorporated herein by reference). When not documented the constants canbe measured using various analytical methods (see “Metal Complexes inAqueous Solutions”, Martel and Hancock, edition Modem InorganicChemistry, p. 226-228, incorporated herein by reference).

It has been found that effective chelants need to have a high affinityfor copper in order to preferentially bind copper found in hair.However, it has been found that also important to efficacy is theability for the chelant to penetrate inside the hair fibers rapidlyduring the shampoo lathering process (which typically lasts between 30seconds and 1 minute). The copper to be removed is inside the hair andthe chelant needs to penetrate inside hair and form a strongcopper-chelant complex. This copper-chelant complex needs to be watersoluble and thus easily removed during the rinsing process. To be ableto do this, two additional parameters have been shown to be importantfor chelant efficacy. These are log P, the octanol/water partitioningcoefficient, and the molecular weight of the chelant. Both are relatedto the ability of the chelant to penetrate into hair and also form awater soluble copper-chelant complex

The one or more chelants for use in the shampoo composition may beselected from the group consisting of triethylenetetramine,tetraethylenepenatmine, pentaethylenehexamine, tris(2-aminoethyl)amine,ethylenedinitrilotetrapropan-2-ol,1,1′,1″-[[2-hydroxypropyl)imino]bis(2,1-ethanediylnitrilo)]tetrakis-2-propanol,tetraethylenepentaamine-(1-EO), 1,5,9,13-tetraazatridecane, and mixturesthereof.

Table 1 provides relevant properties and performance of the one or morecopper chelants described herein. Details on determination of copperremoving performance is described in the Examples section.

TABLE 1 Properties of representative chelants Copper Removing LogPerformance K_(ML) Chelant from Shampoo Cu Log P MW2,3-Triethylenetetramine 70% 20.1 −2.3 146 (TETA)2,4-Tetraethylenepentamine 60% 22.8 −2.7 189 (TEPA)Pentaethylenehexamine 55% −3.1 232 (PEHA) Tris(2-aminoethyl)amine 45%18.8 −2.2 146 (tren) Ethylenedinitrilotetrapropan- 30% 9.8 −0.2 292 2-ol(EDTP) 1,1,1″,1″′ [(2- No data −0.2 394 hydroxypropyl)imino] collectedbis(2,1- ethanediylnitrilo)]tetrakis- 2-Propanol (Pentrol)Tetraethylenepentaamine-(1- No data −2.9 498 EO) collected1,5,9,13-Tetraazatridecane 15% 17.1 −2.1 188 (Thermine)

The log of the formation constant log K_(ML) of its complex with coppercan be higher than 6, alternatively higher than 8, alternatively higherthan 9, alternatively higher than 10, alternatively higher than 12,alternatively higher than 14, alternatively higher than 16,alternatively higher than 17, alternatively higher than 18, andalternatively higher than 20. The log of the formation constant logK_(ML) of its complex with copper can be from about 6 to about 28,alternatively from about 8 to about 27, alternatively from about 9 toabout 26, alternatively from about 10 to about 25, alternatively fromabout 12 to about 24, alternatively from about 14 to about 24,alternatively from about 16 to about 24, alternatively from about 17 toabout 24, alternatively from about 18 to about 24, and alternativelyfrom about 20 to about 23.

The log P value of the one or more chelants can be from about −5 toabout 2, alternatively from about −4 to about 1, alternatively fromabout −3.5 to about 0, and alternatively from about −2.9 to about −2.5.

The molecular weight of the one or more chelants can be from about 50 toabout 500, alternatively from about 75 to about 400, alternatively fromabout 100 to about 350, alternatively from about 125 to about 325,alternatively from about 140 to about 300, alternatively from about 140to about 200.

The copper removing performance of the shampoo composition is determinedby treating hair with clarifying shampoo containing the correspondingchelant for 20 cycles and comparing the copper content of the haircompared to the same treatment using shampoo without the chelant.

Other chelants that can be used to reduce copper content of hair havethe following general structure:

wherein M is hydrogen or a metal ion;p is 1 or 2;q is 1 or 2; andX is selected from the group containing hydrogen, methyl, ethyl, propyl,—CH₂CH₂OH, —CH₂CH(CH₃)OH), —CH₂CH₂NH₂, —CH₂CH(CH₃) NH₂, —CH₂COOM, or—CH₂CH₂SH, and —CH₂CH(CH₃)SH).Non-limiting examples include iminodiacetic acid,N-(2-hydroxyethyl)iminodiacetic acid, N-methyliminodiacetic acid,N-(2-aminoethyl)iminodiacetic acid, N-propyliminodiacetic acid, andnitrilotriacetic acid.

It is found that treatment with shampoo composition containing 0.1 wt %iminodiacetic acid reduces copper by 40% and shampoo compositioncontaining 0.1 wt % N-(2-hydroxyethyl)iminodiacetic acid reduces copperby 30% after 20 cleaning cycles compared to comparative treatment withshampoo that does not contain the chelant.

B. Detersive Surfactant

The shampoo composition comprises from about 2% to about 50%,alternatively from about 5% to about 25%, alternatively from about 7% toabout 22%, alternatively from about 9% to about 18%, and alternativelyfrom about 11% to about 15% of one or more detersive surfactants byweight of the shampoo composition. The concentration of the detersivesurfactant component in the shampoo composition should be sufficient toprovide the desired cleaning and lather performance.

The one or more detersive surfactants can be selected from the groupconsisting of anionic surfactants, amphoteric or zwitterionicsurfactants, or mixtures thereof. The one or more detersive surfactantscan also be selected from the group consisting of anionic surfactants,cationic surfactants, non-ionic surfactants, amphoteric surfactants, andmixtures thereof. Various examples and descriptions of detersivesurfactants are set forth in U.S. Pat. No. 6,649,155; U.S. PatentApplication Publication No. 2008/0317698; and U.S. Patent ApplicationPublication No. 2008/0206355, which are incorporated herein by referencein their entirety.

Anionic surfactants suitable for use in the compositions are the alkyland alkyl ether sulfates. Other suitable anionic surfactants are thewater-soluble salts of organic, sulfuric acid reaction products. Stillother suitable anionic surfactants are the reaction products of fattyacids esterified with isethionic acid and neutralized with sodiumhydroxide. Other similar anionic surfactants are described in U.S. Pat.Nos. 2,486,921; 2,486,922; and 2,396,278, which are incorporated hereinby reference in their entirety.

Exemplary anionic surfactants for use in the shampoo composition includeammonium lauryl sulfate, ammonium laureth sulfate, triethylamine laurylsulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate,triethanolamine laureth sulfate, monoethanolamine lauryl sulfate,monoethanolamine laureth sulfate, diethanolamine lauryl sulfate,diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate,sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate,potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroylsarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoylsulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroylsulfate, potassium cocoyl sulfate, potassium lauryl sulfate,triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodiumtridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodiumcocoyl isethionate and combinations thereof. In a further embodiment,the anionic surfactant is sodium lauryl sulfate or sodium laurethsulfate.

Suitable amphoteric or zwitterionic surfactants for use in the shampoocomposition include those which are known for use in shampoo or otherpersonal care cleansing. Concentrations of such amphoteric surfactantsrange from about 0.5 wt % to about 20 wt %, and from about 1 wt % toabout 10 wt %. Non limiting examples of suitable zwitterionic oramphoteric surfactants are described in U.S. Pat. Nos. 5,104,646 and5,106,609, which are incorporated herein by reference in their entirety.

Amphoteric detersive surfactants suitable for use in the shampoocomposition include those surfactants broadly described as derivativesof aliphatic secondary and tertiary amines in which the aliphaticradical can be straight or branched chain and wherein one of thealiphatic substituents contains from about 8 to about 18 carbon atomsand one contains an anionic group such as carboxy, sulfonate, sulfate,phosphate, or phosphonate. Exemplary amphoteric detersive surfactantsfor use in the present shampoo composition include cocoamphoacetate,cocoamphodiacetate, lauroamphoacetate, lauroamphodiacetate, and mixturesthereof.

Zwitterionic detersive surfactants suitable for use in the shampoocomposition include those surfactants broadly described as derivativesof aliphatic quaternaryammonium, phosphonium, and sulfonium compounds,in which the aliphatic radicals can be straight or branched chain, andwherein one of the aliphatic substituents contains from about 8 to about18 carbon atoms and one contains an anionic group such as carboxy,sulfonate, sulfate, phosphate or phosphonate. In another embodiment,zwitterionics such as betaines are selected.

Non limiting examples of other anionic, zwitterionic, amphoteric oroptional additional surfactants suitable for use in the shampoocomposition are described in McCutcheon's, Emulsifiers and Detergents,1989 Annual, published by M. C. Publishing Co., and U.S. Pat. Nos.3,929,678, 2,658,072; 2,438,091; 2,528,378, which are incorporatedherein by reference in their entirety.

The shampoo composition may also comprise a cationic conditioningpolymer, an aqueous carrier, and other additional ingredients describedherein.

C. Cationic Conditioning Polymers

The shampoo composition described herein may comprise one or morecationic conditioning polymers. This polymer may be selected from thegroup consisting of (a) a cationic guar polymer, (b) a cationic non-guarpolymer, (c) a cationic tapioca polymer, (d) a cationic copolymer ofacrylamide monomers and cationic monomers, (e) a synthetic,non-crosslinked, cationic polymer, which forms lyotropic liquid crystalsupon combination with the detersive surfactant, and (f) mixturesthereof.

D. Carrier

The shampoo composition further comprises from about 75% to about 98%,alternatively from about 80% to about 98% of a cosmetically acceptablecarrier, by weight of the shampoo composition. The carrier can be anaqueous carrier. The amount and chemistry of the carrier is selectedaccording to the compatibility with other components and other desiredcharacteristic of the product. In an embodiment, the carrier is selectedfrom the group consisting of: water and water solutions of lower alkylalcohols. Lower alkyl alcohols useful herein are monohydric alcoholshaving 1 to 6 carbons, such as ethanol and/or isopropanol. In anembodiment, the cosmetically acceptable carrier is a cosmeticallyacceptable aqueous carrier and is present at a level of from about 20%to about 95%, or from about 60% to about 85%.

The pH of the shampoo composition can be from about pH 3 to about pH 8,alternatively from about pH 4 to about pH 7, and alternatively fromabout pH 5 to about pH 6.

E. Benefit Agent

The shampoo composition may further comprise one or more benefit agents.Exemplary benefit agents include, but are not limited to, siliconeemulsions, anti-dandruff actives, perfume microcapsules, gel networks,colorants, particles, and other insoluble skin or hair conditioningagents such as skin silicones, natural oils such as sun flower oil orcastor oil.

(1). Silicone Emulsion

The silicone emulsions suitable for use herein include emulsions ofinsoluble polysiloxanes prepared in accordance with the descriptionsprovided in U.S. Pat. No. 4,476,282 and U.S. Patent ApplicationPublication No. 2007/0276087. Accordingly, insoluble polysiloxanesreferred to herein for the purpose of the invention includepolysiloxanes such as alpha, omega hydroxy-terminated polysiloxanes oralpha, omega alkoxy-terminated polysiloxanes having a molecular weightwithin the range from about 50,000 to about 500,000 g/mol. As usedherein, “insoluble polysiloxane” means that the water solubility of thepolysiloxane is less than 0.05 wt %. In another embodiment, the watersolubility of the polysiloxane is less than 0.02 wt %, or less than 0.01wt %, or less than 0.001 wt %. According to an embodiment, the insolublepolysiloxane is present in the shampoo composition in an amount withinthe range from about 0.1 wt % to about 3 wt %, based on the total weightof the composition. For example, the insoluble polysiloxane can bepresent in an amount within the range from about 0.2 wt % to about 2.5wt %, or from about 0.4 wt % to about 2.0 wt %, or from about 0.5 wt %to about 1.5 wt %, based on the total weight of the composition.

According to one aspect of the silicone emulsion, the insolublepolysiloxane used herein include alpha, omega hydroxy- oralkoxy-terminated polysiloxanes having a general formula I:R¹—[O—SiR₂]_(n)—OR¹,wherein ‘n’ is an integer, R is a substituted or unsubstituted C₁ to C₁₀alkyl or aryl, and R¹ is a hydrogen or a substituted or unsubstituted C₁to C₁₀ alkyl or aryl. Non-limiting examples of R and R¹ may beindependently selected from alkyl groups such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl,neopentyl, tertpentyl, hexyl such as n-hexyl, heptyl such as n-heptyl,octyl such as n-octyl and isooctyl such as 2,2,4-trimethyl-pentyl, nonylsuch as n-nonyl, decyl such as n-decyl, dodecyl such as n-dodecyl,octadecyl such as n-octadecyl; or aryl groups such as phenyl, naphthyl,anthryl and phenanthryl. In an embodiment, the insoluble polysiloxanehas a general formula H—[O—SiR₂]_(n)—OH.

According to another aspect of the silicone emulsion, the insolublepolysiloxane has an average molecular weight within the range from about50,000 to about 500,000 g/mol. For example, the insoluble polysiloxanemay have an average molecular weight within the range from about 60,000to about 400,000; from about 75,000 to about 300,000; from about 100,000to about 200,000; or the average molecular weight may be about 150,000g/mol.

According to another aspect of the silicon emulsion, total content of acyclic polysiloxane having a general formula:

wherein R is as defined above, and wherein m is 4 or 5, is present inthe silicone emulsion in an amount less than about 2.5 wt % based on thetotal weight of all polysiloxanes. For example, dimethiconol may includesignificant quantities of cyclic polysiloxanes, such asoctamethylcyclotetrasiloxane (D4) and decamethylcyclotetrasiloxane (D5).In an embodiment, the amount of D4 is less than about 2.0%, or less thanabout 1.5%, or less than about 1.0%, or less than about 0.5%, based onthe total weight of all polysiloxanes. In an embodiment, the amount ofD5 is less than about 0.5%, or less than about 0.4%, or less than about0.3%, or less than about 0.2%, based on the total weight of allpolysiloxanes.

According to yet another aspect of the silicone emulsion, the emulsionhas a viscosity up to about 500,000 cPs. For example, the viscosity maybe within the range from about 75,000 to about 300,000, from about100,000 to about 200,000, or about 150,000 cPs.

According to yet another aspect of the silicone emulsion, the insolublepolysiloxane has an average particle size within the range from about 30nm to about 10 micron. The average particle size may be within the rangefrom about 40 nm to about 5 micron, from about 50 nm to about lmicron,from about 75 nm to about 500 nm, or about 100 nm, for example.

The average molecular weight of the insoluble polysiloxane, theviscosity of the silicone emulsion, and the size of the particlecomprising the insoluble polysiloxane are determined by methods commonlyused by those skilled in the art, such as the methods disclosed inSmith, A. L. The Analytical Chemistry of Silicones, John Wiley & Sons,Inc.: New York, 1991. For example, the viscosity of the siliconeemulsion can be measured at 30° C. with a Brookfield viscosimeter withspindle 6 at 2.5 rpm.

According to another aspect of the silicone emulsion, the emulsionfurther includes an anionic surfactant that participates in providinghigh internal phase viscosity emulsions having particle sizes in therange from about 30 nm to about 10 micron. The anionic surfactant isselected from organic sulfonic acids. Most common sulfonic acids used inthe present process are alkylaryl sulfonic acid; alkylarylpolyoxyethylene sulphonic acid; alkyl sulfonic acid; and alkylpolyoxyethylene sulfonic acid. General formulas of the sulfonic acidsare as shown below:R²C₆H₄SO₃H  (II)R²C₆H₄O(C₂H₄O)_(m)SO₃H  (III)R²SO₃H  (IV)R²O(C₂H₄O)_(m)SO₃H  (IV)Where R², which may differ, is a monovalent hydrocarbon radical havingat least 6 carbon atoms. Non-limiting examples of R² include hexyl,octyl, decyl, dodecyl, cetyl, stearyl, myristyl, and oleyl. ‘m’ is aninteger from 1 to 25. Exemplary anionic surfactants include but are notlimited to octylbenzene sulfonic acid; dodecylbenzene sulfonic acid;cetylbenzene sulfonic acid; alpha-octyl sulfonic acid; alpha-dodecylsulfonic acid; alpha-cetyl sulfonic acid; polyoxyethylene octylbenzenesulfonic acid; polyoxyethylene dodecylbenzene sulfonic acid;polyoxyethylene cetylbenzene sulfonic acid; polyoxyethylene octylsulfonic acid; polyoxyethylene dodecyl sulfonic acid; andpolyoxyethylene cetyl sulfonic acid. Generally, 1 to 15% anionicsurfactant is used in the emulsion process. For example, 3-10% anionicsurfactant can be used to obtain an optimum result.

The silicone emulsion may further include an additional emulsifiertogether with the anionic surfactant, which along with the controlledtemperature of emulsification and polymerization, facilitates making theemulsion in a simple and faster way. Non-ionic emulsifiers having ahydrophilic lipophilic balance (HLB) value of 10 to 19 are suitable andinclude polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ethersand polyoxyalkylene sorbitan esters. Some useful emulsifiers having anHLB value of 10 to 19 include, but are not limited to, polyethyleneglycol octyl ether; polyethylene glycol lauryl ether; polyethyleneglycol tridecyl ether; polyethylene glycol cetyl ether; polyethyleneglycol stearyl ether; polyethylene glycol nonylphenyl ether;polyethylene glycol dodecylphenyl ether; polyethylene glycol cetylphenylether; polyethylene glycol stearylphenyl ether; polyethylene glycolsorbitan monostearate; and polyethylene glycol sorbitan monooleate.

In accordance with another embodiment, the composition may furthercomprise an anti-dandruff active, which may be an anti-dandruff activeparticulate.

F. Other Components

The shampoo composition can also additionally comprise any suitableoptional ingredients as desired. Such optional ingredients should bephysically and chemically compatible with the components of thecomposition, and should not otherwise unduly impair product stability,aesthetics, or performance. The CTFA Cosmetic Ingredient Handbook, TenthEdition (published by the Cosmetic, Toiletry, and Fragrance Association,Inc., Washington, D.C.) (2004) (hereinafter “CTFA”), describes a widevariety of nonlimiting materials that can be added to the compositionherein.

In accordance with another embodiment of the invention, a method ofmaking a shampoo composition comprising a detersive surfactant, acationic conditioning polymer, a chelant, and a carrier is provided. Themethod includes (i) combining the detersive surfactant and the cationicconditioning polymer in suitable carrier, and (ii) combining a chelantand a carrier composition that includes a product of step (i) to formthe shampoo composition.

In an embodiment, the shampoo composition has a viscosity of 4,000 cP to20,000 cP, or from about 6,000 cP to about 12,000 cP, or from about8,000 cP to about 11,000 cP, measured at 26.6° C. with a Brookfield R/SPlus Rheometer at 2 s⁻¹. cP means centipoises.

Also described herein is a method of inhibiting copper deposition onhair and facilitating the removal of copper deposited on hair comprisingapplying to the hair a shampomo composition described herein and rinsingthe shampoo composition from the hair.

Inhibition of copper deposition on hair and facilitation of the removalof copper deposited on hair may also be achieved by applying a leave-ontreatment to the hair after rinsing the conditioner from the hair. Theleave-on treatment may deliver consumer desired conditioning in additionto inhibiting the deposition of copper (i.e. from the water used torinse) on the hair. The leave-on treatment described herein may comprisefrom about 0.025% to about 0.50%, alternatively from about 0.05% toabout 0.25% of one or more chelants described herein, by weight of theleave-on treatment. The leave-on treatment may also comprise one or morerheology modifiers and an aqueous carrier.

The shampoo composition can be prepared by conventional formulation andmixing techniques. It will be appreciated that other modifications ofthe shampoo composition within the skill of those in the hair careformulation art can be undertaken without departing from the spirit andscope of this invention. All parts, percentages, and ratios herein areby weight unless otherwise specified. Some components may come fromsuppliers as dilute solutions. The amount stated reflects the weightpercent of the active material, unless otherwise specified.

Test Methods Shampoo Treatment Protocol

All testing are performed on colored hair switches (see Method ofMeasurement of Copper on Hair below) weighing approximately 4.0 gramsand having a length of approximately 6 inches. The hair switches arecommercially available from IHIP (International Hair Importers). Threehair switches per sampoo composition are used. An amount of 0.20 g ofshampoo is spread via a syringe onto separate hair switch. That is, thedosage is 0.10 g of shampoo per g of hair. Each application consists ofadding shampoo to the hair, milking for 30 seconds followed by rinsingfor 30 seconds. Shampoo is then reapplied (0.1 g/g), milked for 30seconds and rinsed for 30 seconds. Excess water is squeezed from thehair switches and left to air dry or treated with a rinse-offconditioner and/or a leave-on treatment composition. This protocol isrepeated for a number of times/cycles (as indicated in the tables below,which describe the details of hair treatments).

Method of Measurement of Copper on Hair

The following test method is used to assess the ability of thecompositions and regimens to remove copper from the hair and to inhibitcopper deposition onto the hair.

Hair switches are colored once with an oxidative hair colorant. An extrablonde shade is used for the testing. The hair switches are washed for10 or 20 repeat wash cycles in tap water containing 7 grains per gallonwater hardness (Ca/Mg) and 0.06 μg/g copper ions. Each wash cycleconsists of two applications of 0.1 g/g a shampoo to the hair switches.Each application consists of adding shampoo to the hair, milking for 30secs followed by rinsing for 30 secs. Shampoo is then reapplied 0.1 g/g,milked for 30 secs, rinsed for 30 secs and then dried in a heat box (60°C.) until dry.

Samples of 100 mg of hair are digested overnight with 2 ml of highpurity concentrated nitric acid. The digestive mixture also contains 150μL of 100 μg/g Yttrium internal standard (Inorganic Ventures,Christianburg, Va., USA). Following digestion, samples are heated to70-80° C. for one hour, cooled to room temperature and diluted to 15 mLwith deionized water. Copper content of the hair switches is determinedby inductively coupled plasma atomic spectroscopy (ICP-OES)). For eachleg, 3 different samples are analyzed.

EXAMPLES & DATA

The following are non-limiting examples of the shampoo compositiondescribed herein. The examples are given solely for the purpose ofillustration and are not to be construed as limitations of the shampoocomposition, as many variations thereof are possible without departingfrom the spirit and scope of the shampoo composition, which would berecognized by one of ordinary skill in the art.

The shampoo composition described herein is generally prepared byconventional methods. Such methods typically involve mixing of theingredients in one or more steps to a relatively uniform state, with orwithout heating, cooling, application of vacuum, and the like. Thecompositions are prepared such as to optimize stability (physicalstability, chemical stability, photostability) and/or delivery of theactive materials. The shampoo composition may be in a single phase or asingle product, or the shampoo composition may be in a separate phasesor separate products. If two products are used, the products may be usedtogether, at the same time, or sequentially. Sequential use may occur ina short period of time, such as immediately after the use of oneproduct, or it may occur over a period of hours or days.

In order to minimize the variability of the resulting copper content onhair that is related to (a) lot-to-lot viariability due to hair switchesand (b) day-to-day variability of the water used during shampoo andconditioner treatments, a single lot of hair switches is used for eachexperimental series and a separate control experiment/treatment is runfor each experimental series (see below).

Experimental Series I

Investigation of treatments with clarifying shampoos containing simplesurfactants and 2,3-Triethylenetetramine.

Ex. 1 Control Ex. 2 Components Wt % Wt % Sodium Laureth-1 Sulfate¹ 10.5010.50 Sodium Lauryl Sulfate² 1.50 1.50 Cocamidopropyl betaine 1.00 1.00Sodium benzoate 0.25 0.25 Citric Acid 0.70 0.70Methylchloroisothiazolinone/ 0.0005 0.0005 Methylisothiazolinone³ Sodiumchloride 1.00 1.00 Tetrasodium EDTA dihydrate 0.16 0.162,3-Triethylenetetramine (TETA) 0.00 0.10 Deionized water Q.S. Q.S. pHadjusted to 6.0 6.0 ¹Sodium laureth-3-sulfate available from BASF asStandapol ES-3 (28 wt. % active). ²Sodium Lauryl Sulfate available fromBASF as Standapol WAQ-LC (29 wt. % active). ³Kathon CG available fromDow (1.5 wt % active).

Results of Experimental Series I

Composition of Ex. 1 Ex. 2 Summary Description Control ClarifyingClarifying shampoo of Composition shampoo with simple with simplesurfac- surfactant tant and chelant Concentration of 0.0% 0.10% Chelantin Shampoo Chelant used — 2,3- Triethylenetetramine Shampoo pH 6.0 6.0Shampoo cycles 10 10 Average final copper 84 33 concentration in hair(ppm) Standard deviation 4.2 1.1 Relative content of 100 33 Coppercontent on hair after treatment (versus control shampoo treatment)

Chelant 2,3-Triethylenetetramine contributes to significant reduction ofcopper content on hair after 10 shampoo cycle treatments compared totreatment with shampoo composition that does not comprise the chelant.

Experimental Series II

Investigation of treatments with clarifying shampoos containing simplesurfactants and 2,3-Triethylenetetramine in two different pH values.

Ex. 3 Ex. 4 Control Control Ex. 5 Ex. 6 Components Wt % Wt % Wt % Wt %Sodium Laureth-1 Sulfate¹ 10.50 10.50 10.50 10.50 Sodium Lauryl Sulfate²1.50 1.50 1.50 1.50 Cocamidopropyl betaine 1.00 1.00 1.00 1.00 Sodiumbenzoate 0.25 0.25 0.25 0.25 Citric Acid 0.70 1.00 0.70 1.00Methylchloroisothiazolinone/ 0.0005 0.0005 0.0005 0.0005Methylisothiazolinone³ Sodium chloride 1.00 1.00 1.00 1.00 TetrasodiumEDTA dihydrate 0.16 0.16 0.16 0.16 2,3-Triethylenetetramine 0.00 0.000.10 0.10 Deionized water Q.S. Q.S. Q.S. Q.S. to 100 to 100 to 100 to100 pH adjusted to 6.0 4.25 6.0 4.25 ¹Sodium laureth-3-sulfate availablefrom BASF as Standapol ES-3 (28 wt. % active). ²Sodium Lauryl Sulfateavailable from BASF as Standapol WAQ-LC (29 wt. % active). ³Kathon CGavailable from Dow (1.5 wt % active).

Results of Experimental Series II

Composition of Ex. 3 Ex. 4 Ex. 5 Ex. 6 Summary Description ControlControl Clarifying shampoo Clarifying shampoo of Composition Clarifyingshampoo Clarifying shampoo with simple surfactant with simple surfactantwith simple surfactant with simple surfactant and chelant and chelantConcentration of 0.0% 0.0% 0.10% 0.10% Chelant in Shampoo Chelant used —— 2,3- 2,3- Triethylenetetramine Triethylenetetramine Shampoo pH 6.04.25 6.0 4.25 Shampoo cycles 20 20 20 20 Average final copper 92 62 3436 concentration in hair (ppm) Standard deviation 11 4.8 3.1 3.6Relative content of 100.0 67 v. 39 v. 37 v. Copper content on hairControl Control Control after treatment (versus control shampootreatment)

The presence of 2,3-Triethylenetetramine acid contributes to aneffective removal of copper from hair after 20 shampoo cycles both atlow and a higher pH value. Without the chelant, lower pH shows highercopper removal from hair.

Experimental Series III

Investigation of treatments with clarifying shampoos containing simplesurfactants (pH=6) and various chelants described herein.

Ex. 7 Control Ex. 8 Ex. 9 Ex. 10 Ex. 11 Components Wt % Wt % Wt % Wt %Wt % Sodium Laureth-1 Sulfate¹ 10.50 10.50 10.50 10.50 10.50 SodiumLauryl Sulfate² 1.50 1.50 1.50 1.50 1.50 Cocamidopropyl betaine 1.001.00 1.00 1.00 1.00 Sodium benzoate 0.25 0.25 0.25 0.25 0.25 Citric Acid0.70 0.70 0.70 1.00 1.00 Methylchloroisothiazolinone/ 0.0005 0.00050.0005 0.0005 0.0005 Methylisothiazolinone³ Sodium chloride 1.00 1.001.00 1.00 1.00 Tetrasodium EDTA dihydrate 0.16 0.16 0.16 0.16 0.162,3-Triethylenetetramine 0.00 0.10 0.00 0.00 0.00 Tetraethylenepentamine0.00 0.00 0.10 0.00 0.00 Tris(2-aminoethyl)amine 0.00 0.00 0.00 0.000.00 Pentaethylenehexamine 0.00 0.00 0.00 0.00 0.10 Deionized water Q.S.Q.S. Q.S. Q.S. Q.S. to 100 to 100 to 100 to 100 to 100 pH adjusted to6.0 6.0 6.0 6.0 6.0 ¹Sodium laureth-3-sulfate available from BASF asStandapol ES-3 (28 wt. % active). ²Sodium Lauryl Sulfate available fromBASF as Standapol WAQ-LC (29 wt. % active). ³Kathon CG available fromDow (1.5 wt % active).

Results of Experimental Series III

Composition of Ex. 7 Ex. 8 Ex. 9 Summary Description Control Clarifyingshampoo Clarifying shampoo of Composition Clarifying shampoo with simplesurfactant with simple surfactant with simple surfactant and chelant andchelant Concentration of 0.0% 0.10% 0.10% Chelant in Shampoo Chelantused — 2,3- Tetraethylenepentamine Triethylenetetramine Chelant Class —Class III Class III Shampoo pH 6.0 6.0 6.0 Shampoo cycles 20 20 20Average final copper 115 37 49 concentration in hair (ppm) Standarddeviation 14 2.8 2.7 Relative content of 100 32 43 Copper content onhair after treatment (versus control shampoo treatment) Composition ofEx. 10 Ex. 11 Summary Description Clarifying shampoo Clarifying shampooof Composition with simple surfactant with simple surfactant and chelantand chelant Concentration of 0.10% 0.10% Chelant in Shampoo Chelant usedTris(2- Pentaethylenehexamine aminoethyl)amine Shampoo pH 6.0 6.0Shampoo cycles 20 20 Average final copper 62 53 concentration in hair(ppm) Standard deviation 3.8 10.5 Relative content of 54 46 Coppercontent on hair after treatment (versus control shampoo treatment)

All chelants from Class III evaluated in a 20 cycle cleaning treatmentusing a clarifying shampoo containing simple surfactants shows reductionof copper hair content compared to the control shampoo treatment.2,3-Triethylenetetramine and Tetraethylenepentamine show more effectivetreatements.

Experimental Series IV

Investigation of treatments with clarifying shampoos containing simplesurfactants (pH=6) and ethylenedinitrilotetrapropan-2-ol chelant.

Ex. 12 Control Ex. 13 Components Wt % Wt % Sodium Laureth-1 Sulfate¹10.50 10.50 Sodium Lauryl Sulfate² 1.50 1.50 Cocamidopropyl betaine 1.001.00 Sodium benzoate 0.25 0.25 Citric Acid 0.70 0.70Methylchloroisothiazolinone/ 0.0005 0.0005 Methylisothiazolinone³ Sodiumchloride 1.00 1.00 Tetrasodium EDTA dihydrate 0.16 0.16Ethylenedinitrilotetrapropan-2-ol 0.00 0.40 Deionized water Q.S. Q.S. to100 to 100 pH adjusted to 6.0 6.0 ¹Sodium laureth-3-sulfate availablefrom BASF as Standapol ES-3 (28 wt. % active). ²Sodium Lauryl Sulfateavailable from BASF as Standapol WAQ-LC (29 wt. % active). ³Kathon CGavailable from Dow (1.5 wt % active).

Results of Experimental Series IV

Composition of Ex. 12 Ex. 13 Summary Description Control ClarifyingClarifying shampoo of Composition shampoo with simple with simplesurfac- surfactant tant and chelant Concentration of 0.00% 0.40% Chelantin Shampoo Chelant used — Ethylene- dinitrilotetra- propan-2-ol ShampoopH 6.0 6.0 Shampoo cycles 20 20 Average final copper 70 50 concentrationin hair (ppm) Standard deviation 2.6 0.4 Relative content of 100 71Copper content on hair after treatment (versus control shampootreatment)

The presence of ethylenedinitrilotetrapropan-2-ol acid (at aconcentration of 0.40 wt %) contributes to an effective removal ofcopper from hair after 20 shampoo cycles compared to the correspondingtreatment with control shampoo that does not contain the chelant.

Experimental Series V

Investigation of treatments with clarifying shampoos containing simplesurfactants, a rheology modifier and tris-2-aminoethylamine.

Ex. 14 Control Ex. 15 Components Wt % Wt % Sodium Laureth-3 Sulfate¹6.00 6.00 Sodium Lauryl Sulfate² 9.50 9.50 Cocamidopropyl betaine 1.881.88 Tetrasodium EDTA dihydrate 0.16 0.16 Citric Acid (Anhydrous) 0.280.28 Sodium benzoate 0.25 0.25 Methylchloroisothiazolinone/ 0.00050.0005 Methylisothiazolinone³ Sodium chloride 0.57 0.57Hydroxypropylmethylcellulose 0.25 0.25 Tris-2-aminoethylamine 0.00 0.10Perfume 0.40 0.40 Distilled Water Q.S. Q.S. ¹Sodium laureth-3-sulfateavailable from BASF as Standapol ES-3 (28 wt. % active). ²Sodium LaurylSulfate available from BASF as Standapol WAQ-LC (29 wt. % active).³Kathon CG available from Dow (1.5 wt % active).

Results of Experimental Series V

Composition of Ex. 14 Ex. 15 Summary Description Control ClarifyingClarifying shampoo of Composition shampoo with simple with simplesurfac- surfactant and tant, a Rheology Rheology Modifier Modifier and achelant Concentration of 0.00% 0.10% Chelant in Shampoo Chelant used —Tris-2- aminoethylamine Shampoo pH 6.0 6.0 Shampoo cycles 10 10 Averagefinal copper 94 62 concentration in hair (ppm) Standard deviation 15 9.5Relative content of 100 66 Copper content on hair after treatment(versus control shampoo treatment)

The presence of tris-2-aminoethylamine acid contributes to an effectiveremoval of copper from hair after 10 shampoo cycles compared to thecorresponding treatment with control clarifying shampoo that does notcontain the chelant.

Experimental Series VI

Investigation of treatments with clarifying shampoos containing simplesurfactants, a rheology modifier and chelants having 2-aminodiaceticacid molecular structures.

Ex. 16 Control Ex. 17 Ex. 18 Components Wt % Wt % Wt % Sodium Laureth-3Sulfate¹ 6.00 6.00 6.00 Sodium Lauryl Sulfate² 9.50 9.50 9.50Cocamidopropyl betaine 1.88 1.88 1.88 Tetrasodium EDTA dihydrate 0.160.16 0.16 Citric Acid (Anhydrous) 0.28 0.28 0.28 Sodium benzoate 0.250.25 0.25 Methylchloroisothiazolinone/ 0.0005 0.0005 0.0005Methylisothiazolinone³ Sodium chloride 0.57 0.57 0.57Hydroxypropylmethylcellulose 0.25 0.25 0.25 Iminodiacetic acid 0.00 0.100.00 N-(2-hydroxyethyl)iminodiacetic acid 0.00 0.00 0.10 Perfume 0.400.40 0.40 Distilled Water Q.S. Q.S. Q.S. ¹Sodium laureth-3-sulfateavailable from BASF as Standapol ES-3 (28 wt. % active). ²Sodium LaurylSulfate available from BASF as Standapol WAQ-LC (29 wt. % active).³Kathon CG available from Dow (1.5 wt % active).

Results of Experimental Series VI

Composition of Ex. 16 Ex. 17 Ex. 18 Summary Description ControlClarifying Clarifying shampoo Clarifying shampoo of Composition shampoowith simple with simple surfactant, with simple surfactant, surfactantand a Rheology Modifier a Rheology Modifier Rheology Modifier and achelant and a chelant Concentration of 0.00% 0.10% 0.10% Chelant inShampoo Chelant used — Iminodiacetic acid N-(2-hydroxyethyl)iminodiacetic acid Shampoo pH 6.0 6.0 6.0 Shampoo cycles 2020 20 Average final copper 84 51 56 concentration in hair (ppm) Standarddeviation 6.5 2.7 1.7 Relative content of 100 61 67 Copper content onhair after treatment (versus control shampoo treatment)

The presence of chelants having 2-aminodiacetic acid molecularstructures contributes to an effective removal of copper from hair after20 shampoo cycles compared to the corresponding treatment with controlclarifying shampoo that does not contain the chelant.

Experimental Series VII

Investigation of treatments using shampoos and rinse-off conditioner andleave-on treatments containing 2,3-Triethylenetetramine chelant.

Conditioning Shampoo Compositions

Ex. 19 Control Ex. 20 Components Wt % Wt % Sodium Laureth-3 Sulfate¹6.10 6.10 Sodium Lauryl Sulfate² 4.00 4.00 Cocoamide MEA³ 0.90 0.90 Guarhydroxypropyltrimonium chloride⁴ 0.25 0.25 Glycol distearate 1.50 1.50Dimethicone⁵ 1.00 1.00 Tetrasodium EDTA dihydrate 0.16 0.16 Citric Acid(Anhydrous) 0.18 0.18 Sodium benzoate 0.27 0.27Methylchloroisothiazolinone/ 0.0006 0.0006 Methylisothiazolinone⁶ Sodiumchloride 0.20 0.20 Hydrochloric acid (6N) 0.06 0.062,3-Triethylenetetramine (TETA) 0.00 0.10 Perfume 0.40 0.40 DistilledWater Q.S. Q.S. ¹Sodium laureth-3-sulfate available from BASF asStandapol ES-3 (28 wt. % active). ²Sodium Lauryl Sulfate available fromBASF as Standapol WAQ-LC (29 wt. % active). ³Cocamide MEA available fromBASF as Comperlan CMEA (85 wt. % active). ⁴Jaguar C-500 available fromAshland. ⁵Silicone oil with viscosity of 330.000 cP ⁶Kathon CG availablefrom Dow (1.5 wt % active).

Clarifying Shampoo Compositions

Ex. 19(a) Control Ex. 21 Components Wt % Wt % Sodium Laureth-3 Sulfate¹6.00 6.00 Sodium Lauryl Sulfate² 9.50 9.50 Cocamidopropyl betaine 1.881.88 Tetrasodium EDTA dehydrate 0.16 0.16 Citric Acid (Anhydrous) 0.280.28 Sodium benzoate 0.25 0.25 Methylchloroisothiazolinone/ 0.00050.0005 Methylisothiazolinone³ Sodium chloride 0.57 0.57Hydroxypropylmethylcellulose 0.25 0.25 2,3-Triethylenetetramine (TETA)0.0 0.10 Perfume 0.40 0.40 Distilled Water Q.S. Q.S. ¹Sodiumlaureth-3-sulfate available from BASF as Standapol ES-3 (28 wt. %active). ²Sodium Lauryl Sulfate available from BASF as Standapol WAQ-LC(29 wt. % active). ³Kathon CG available from Dow (1.5 wt % active).

Hair Repair Shampoo Compositions

Ex. 22 Control Ex. 23 Components Wt % Wt % Ammonium lauryl sulfate 16.0016.00 Cocoamide MEA¹ 0.8 0.8 Cetyl alcohol 0.9 0.9 Polyquatemium-10² 0.50.5 Polyethylene glycol 7M³ 0.10 0.10 Dimethicone⁴ 2.00 2.00 Glycoldistearate 1.50 1.50 Sodium benzoate 0.25 0.25 Disodium EDTA 0.13 0.13Citric acid 0.04 0.04 Sodium citrate dehydrate 0.45 0.45 Sodium chloride0.03 0.03 Methylchloroisothiazolinone/ 0.0005 0.0005Methylisothiazolinone⁵ Perfume 0.50 0.50 2,3-Triethylenetetramine (TETA)0.00 0.10 Distilled Water Q.S. Q.S. ¹Cocamide MEA available from BASF asComperlan CMEA (85 wt. % active). ²Quaternized hydroxyethyl celluloseavailable from Dow Unival LR30M. ³Available by Dow. ⁴Silicone oil withviscosity of 330.000 cP. ⁵Kathon CG available from Dow (1.5 wt %active).

Smoothing Rinse-Off Conditioner Compositions

Ex. 24 Control Ex. 25 Components Wt % Wt % Stearyl alcohol 2.32 2.32Cetyl alcohol 0.93 0.93 Dicetyldimonium chloride 0.34 0.34Behentrimonium methosulfate 1.16 1.16 Propylene glycol 0.16 0.16Isopropyl alcohol 0.28 0.28 Disodium EDTA Dihydrate 0.13 0.13 Terminalamodimethicone¹ 0.75 0.75 Methylchloroisothiazolinone/ 0.0005 0.0005Methylisothiazolinone² Benzyl alcohol 0.40 0.40 2,3-Triethylenetetramine(TETA) 0.00 0.10 Distilled Water Q.S. Q.S. ¹Terminal amodimethicone withvisc. Of 10,000 cP at 25° C. is available by Momentive PerformanceMaterials. ²Kathon CG available from Dow (1.5 wt % active)

Volumizing Rinse-Off Conditioner Compositions

Ex. 25(a) Control Ex. 26 Components Wt % Wt % Hydroxypropyl guar¹ 0.350.35 DTDMAC (Quatemium-18²) 0.75 0.75 Stearamidopropyldimethylamine 1.001.00 Glyceryl monostearate 0.25 0.25 Emulsifying wax NF (Polywax NF)0.50 0.50 Cetyl alcohol 1.20 1.20 Stearyl alcohol 0.80 0.80 Oleylalcohol 0.25 0.25 Citric acid 0.13 0.13 EDTA 0.10 0.10 Terminalamodimethicone³ 0.50 0.50 2,3-Triethylenetetramine (TETA) 0.00 0.10Methylchloroisothiazolinone/ 0.0005 0.0005 Methylisothiazolinone⁴ Benzylalcohol 0.4 0.4 Distilled Water Q.S. Q.S. ¹Jaguar HP-105 supplied byRhodia ²Diatallowdimethylammonium chloride ³Terminal amodimethicone withvisc. Of 10,000 cP at 25° C. is available by Momentive PerformanceMaterials. ⁴Kathon CG available from Dow (1.5 wt % active).

Hair Repair Rinse-Off Conditioner Compositions

EX. 27 Control EX. 28 Components Wt % Wt % Behentrimonium chloride 2.282.28 Stearyl alcohol 4.64 4.64 Cetyl alcohol 0.93 0.93 Isopropyl alcohol0.57 0.57 Disodium EDTA Dihydrate 0.13 0.13 Dimethicone¹ 4.20 4.20Sodium hydroxide 0.02 0.02 Methylchloroisothiazolinone/ 0.0005 0.0005Methylisothiazolinone² Benzyl alcohol 0.40 0.40 2,3-Triethylenetetramine0.00 0.10 Distilled Water Q.S. Q.S. ¹Mixture of silicone gum andsilicone oil XF49-B1747 available from Momentive Performance Materials.²Kathon CG available from Dow (1.5 wt % active).

Leave-On Treatment Composition

Ex. 29 Components Wt % Amodimethicone and Cetrimonium chloride andTrideceth-12¹ 0.35 Polyquatemium-11² 0.75 PEG-40 Hydrogenated castor oil0.50 PPG-2 Methyl ether 0.5 DMDM Hydantoin 0.20 Disodium EDTA 0.14Poysorbate 80 0.12 Aminomethyl propanol 0.1 Citric acid anhydrous 0.082,3-Triethylenetetramine 0.10 Distilled Water Q.S. ¹Siameter MEM-0949Emulsion available from Dow Corning; it contains 35% aminosilicone²Copolymer of vinylpyrrolidone and quaternized dimethylaminoethylmethacrylate; Gafquat 755 NH available by Ashland

Results of Experimental Series VII

Each treatment (regimen) includes cleaning with conditioning shampoofollowed by a rinse-off conditioner, followed by a leave-on treatmentspray (when indicated).

Shampoo Ex. 19 Control Ex. 20 Ex. 19 Control Ex. 19 Control Composition(SH) Conditioning SH Conditioning SH Conditioning SH Conditioning SHSmoothing Ex. 24 Control Ex. 24 Control Ex. 25 Ex. 24 Control Rinse-offconditioner Smoothing ROC Smoothing ROC Smoothing ROC Smoothing ROCcomposition (ROC) Leave-on treatment No LOT No LOT No LOT Ex. 29 LOTcomposition (LOT) Summary SH Control SH w/chelant SH Control SH ControlDescription of ROC Control ROC Control ROC w/chelant ROC ControlComposition No LOT No LOT No LOT LOT w/chelant Concentration 0% in SH0.1% in SH 0% in SH 0% in SH of Chelant 0% in ROC 0% in ROC 0.1% in ROC0% in ROC No LOT No LOT No LOT 0.1% in LOT Chelant used — 2,3- 2,3- 2,3-Triethylenetetramine Triethylenetetramine Triethylenetetramine Cycles 2020 20 20 Average final copper 84 30 25 43 concentration in hair (ppm)Standard deviation 5.6 2.1 1.7 0.2 Relative content of 100 36 v. 30 v.51 v. Copper content on hair Treatment AM Treatment AM Treatment AMafter treatment (versus control shampoo treatment) Shampoo Ex. 21 Ex.19(a) Control Ex. 23 Ex. 22 Control Composition (SH) Clarifying SHClarifying SH Repair SH Repair SH Rinse-off conditioner Ex. 25(a)Control Ex. 26 Ex. 27 Control Ex. 28 composition (ROC) Volumizing ROCVolumizing ROC Repair ROC Repair ROC Leave-on treatment No LOT No LOT NoLOT No LOT composition (LOT) Summary SH w/chelant SH Control SHw/chelant SH Control Description of ROC Control ROC w/chelant ROCControl ROC w/chelant Composition No LOT No LOT No LOT Concentration0.1% in SH 0% in SH 0.1% in SH 0.1% in SH of Chelant 0% in ROC 0.1% inROC 0% in ROC 0% in ROC No LOT No LOT No LOT No LOT Chelant used — 2,3-2,3- 2,3- Triethylenetetramine Triethylenetetramine TriethylenetetramineCycles 20 20 20 20 Average final copper 32 28 35 26 concentration inhair (ppm) Standard deviation 1.6 3.4 4.5 0.7 Relative content of 35 v.30 v. 38 v. 28 v. Copper content on hair Treatment AM Treatment AMTreatment AM Treatment AM after treatment (versus control shampootreatment)

Addition of 2,3-Triethylenetetramine in any of the products of theregimen contributes to an effective removal of copper from hair after 20conditioning shampoo/rinse-off conditioner/leave-on treatment regimencycles compared to the corresponding treatment with control conditioningshampoo/control rinse-off conditioner. The regimen where the chelant isadded in the leave-on treatment is particulary effective in removingcopper form hair.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A method comprising: a. inhibiting copperdeposition on hair and facilitating the removal of copper deposited onhair by applying to the hair the shampoo composition comprising: i. fromabout 0.005% to about 5% of one or more chelants, by weight of theshampoo composition, wherein the one or more chelants have a molecularstructure as follows:

wherein n is 2 or 3; m is 1, 2, 3, or 4; and Y and Z are independentlyselected from the group consisting of hydrogen, methyl, ethyl, propyl,butyl, pentyl, —CH₂CH₂OH, —CH₂CH(CH₃)OH), —CH₂CH₂NH₂, —CH₂CH(CH₃)NH₂,and combinations thereof; and wherein the one or more chelantscomprise:
 1. log of the formation constant log K_(ML) of its complexwith copper is higher than 6;
 2. log P value is from about −5 to about2; and
 3. molecular weight of from about 50 to about 500; ii. from about2% to about 50% of one or more detersive surfactants, by weight of theshampoo composition; and iii. from about 75% to about 98% of an aqueouscarrier, by weight of the shampoo composition; iv. a pH of about 3 toabout 8; wherein the one or more chelants penetrates inside a hair fiberforming a copper-chelant complex; b. rinsing the shampoo composition andthe copper-chelant complex from the hair thereby removing the copperfrom the hair.
 2. The method of claim 1, wherein the one or moredetersive surfactants comprises an anionic surfactant selected from thegroup consisting of ammonium lauryl sulfate, include ammonium laurylsulfate, ammonium laureth sulfate, triethylamine lauryl sulfate,triethylamine laureth sulfate, triethanolamine lauryl sulfate,triethanolamine laureth sulfate, monoethanolamine lauryl sulfate,monoethanolamine laureth sulfate, diethanolamine lauryl sulfate,diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate,sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate,potassium laureth sulfate, sodium lauryl sarcosinate, sodium lauroylsarcosinate, lauryl sarcosine, cocoyl sarcosine, ammonium cocoylsulfate, ammonium lauroyl sulfate, sodium cocoyl sulfate, sodium lauroylsulfate, potassium cocoyl sulfate, potassium lauryl sulfate,triethanolamine lauryl sulfate, triethanolamine lauryl sulfate,monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodiumtridecyl benzene sulfonate, sodium dodecyl benzene sulfonate, sodiumcocoyl isethionate and combinations thereof.
 3. The method of claim 1,wherein the shampoo composition comprises from about 5% to about 25% ofthe one or more detersive surfactants by weight of the shampoocomposition.
 4. The method of claim 1, wherein the shampoo compositioncomprises from about 7% to about 22% of the one or more detersivesurfactants by weight of the shampoo composition.
 5. The method of claim1, wherein the shampoo composition comprises from about 9% to about 18%of the one or more detersive surfactants by weight of the shampoocomposition.
 6. The method of claim 1, wherein the shampoo compositioncomprises from about 11% to about 15% of the one or more detersivesurfactants by weight of the shampoo composition.
 7. The method of claim1, wherein the log P value of the one or more chelants is from about −4to about
 1. 8. The method of claim 1, wherein the log P value of the oneor more chelants is from about −3 to about
 0. 9. The method of claim 1,wherein the molecular weight of the one or more chelants is from about75 to about
 400. 10. The method of claim 1, wherein the molecular weightof the one or more chelants is from about 100 to about
 350. 11. Themethod of claim 1, wherein the molecular weight of the one or morechelants is from about 125 to about
 325. 12. The method of claim 1,wherein the molecular weight of the one or more chelants is from about140 to about
 300. 13. The method of claim 1, wherein the shampoocomposition further comprises a gel network, wherein the gel networkcomprises a fatty alcohol and a surfactant.
 14. The method of claim 1,wherein the shampoo composition comprises from about 0.01% to about 3%of the one or more chelants.
 15. The method of claim 1, wherein theshampoo composition comprises from about 0.01% to about 1% of the one ormore chelants.
 16. The method of claim 1, wherein the shampoocomposition comprises from about 0.01% to about 0.5% of the one or morechelants.
 17. The method of claim 1, wherein the shampoo compositioncomprises from about 0.01% to about 0.1% of the one or more chelants.18. The method of claim 1, wherein the one or more chelants are selectedfrom the group consisting of 2,3-triethylenetetramine,tetraethylenepentamine, 2,4-tetraethylenepentamine,pentaethylenehexamine, tris(2-aminoethyl)amine,ethylenedinitrilotetrapropan-2-ol,1,1′,1″,1′″[2-hydroxypropyl)imino]bis(2,1ethanediylnitrilo)]tetrakis-2-propanol,tetraethylenepentaamine-(1-EO), 1,5,9,13-Tetraazatridecane, and mixturesthereof.
 19. A method comprising: a. inhibiting copper deposition onhair and facilitating the removal of copper deposited on hair byapplying to the hair the shampoo composition comprising: i. from about0.01% to about 1%, by weight of the composition, of a chelant whereinthe chelant consists of 2,3-Triethylenetetramine; ii. from about 5% toabout 25% of one or more detersive surfactants, by weight of the shampoocomposition; iii. a cationic polymer; iv. a silicone; v. from about 75%to about 98% of an aqueous carrier, by weight of the shampoocomposition; vi. a pH of about 3 to about 8; wherein the chelantpenetrates inside a hair fiber forming a copper-chelant complex; b.rinsing the shampoo composition from the hair and the copper-chelantcomplex from the hair thereby removing the copper from the hair.
 20. Themethod of claim 19 wherein the one or more detersive surfactantscomprises ammonium lauryl sulfate; and wherein the cationic polymercomprises Polyquaternium-10.